CN103233362B - Sorbing material of nonwoven surface coupling tannin and preparation method thereof - Google Patents
Sorbing material of nonwoven surface coupling tannin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of sorbing material of nonwoven surface coupling tannin, carboxylic unsaturated monomer is grafted to macromolecule non-woven fabrics base material surface to introduce carboxyl by the method uv induction technology, the catalyzing and condensing of recycling diamine and carboxyl is to introduce amido, then it is converted into schiff bases reactive intermediates tannin coupling is fixed (change) in nonwoven surface to utilize aldehyde activation method, washes away finally by boiling water the sorbing material that (change) tannin and obtained nonwoven surface coupling tannin are fixed in non-coupling; This sorbing material hydrophily is better, and water absorption rate can more than 1000%; Its content of phenolic hydroxyl groups and water absorption rate are adjustable on a large scale, to protein, there is stronger adsorption capacity, when the concentration of gelatin in the aqueous solution or model wine is between 100-400mg/L, its equilibrium adsorption capacities, between 14.7-50.9mg/g, reaches adsorption equilibrium at 1 hours.
Description
Technical field
The present invention relates to a kind of sorbing material at nonwoven surface coupling tannin and preparation method thereof, belong to adsorbing separation field.
Background technology
The absorption of protein in water-based fluid, separation and removing sulfuldioxide in natural product extraction with deep processing in being separated and removing of protein, plant base beverage haze active proteins remove and the beverage products such as drinks use the method precipitated with the gelatin to remove haze active plant polyphenol after remain gelatin the field such as to remove again there is great practical value.
First, the exploitation of functional natural products is a field having vigor, tie up lot of documents in general database and relate to tangerine peel polysaccharide, opotism polysaccharide, pumpkin water-soluble polysaccharide, Oolong Tea Polysaccharides, Mytilus galloprovincialis polysaccharide, Polysaccharide from Portulaca oleracea, Polysaccharide from Osmunda japonica Thunb, acorn starch and the hyaluronic purifying of fermentation, what its key problem in technology all related to foreign protein in extract removes that (Jiang Xiao wriggles, papain removes the research of tangerine peel polysaccharide foreign protein, Agrifood science and technology, 2012,6(1): 14-16; Lu Huiling etc., the progress that in plant polyose, albumen removes, research and development of natural products, 2008,20:185-189. etc.).Jatropha curcus seeds of trees grouts are a kind of good feed resources, if but active toxalbumin contained by it does not remove and just can only work as fertilizer use, significantly reduce its value (Xiao Jianhui etc., ultrafiltration removes the research of barbadosnut seed grouts toxalbumin, China's feed, 2009, (15): 36-40).
Secondly, the plant base beverage being representative with beer, fruit wine and fruit juice relates to a huge industry, and formation muddy in these products has a significant impact its quality tool.Muddy type mainly muddy, the biological haze of inorganic salts and protein-polyphenol interacts the muddiness formed, wherein especially with the 3rd class muddiness, product is had the greatest impact, haze active (sensitivity) albumen of its Crack cause mainly in product is as gliadin Pro-rich and glutamic acid units, easily with haze active plant polyphenol (tannin) compound in product, be cross-linked and form muddiness and even precipitate, and then affect the outward appearance of product, local flavor and value preserving phase.(greatly) gliadin contains the proline of 15-20%, and [in the maltol leach protein of Nanjing, proline and content of glutamic acid are respectively 13.8% and 39.3%(Jin Bei etc., the research of different alcohol soluble protein in malt compositional difference, China brewages, 2011,235 (10): 29-32) from the protein that cider is separated with grape pip ,], also contain the proline (KarlJ.Siebert of 5% and 9.5% respectively, Haze formation in beverages LWT, 2006 (30): 987-994; Michel Lopez et al. Methods for the prevention or reduction of haze in beverages, US 8119171B2), thus the plant base beverage produced with these raw materials has high muddy risk, therefore, the adjustment of haze active proteins content wherein and selectively removing are also just become to the key of related industry skill upgrading.
Besides, for plant base beverage removing as haze active plant polyphenol in beer, extensively adopt at present and add gelatin, fish glue [Pro-rich and glutamic acid, cattle hide gelatin is respectively containing 13.1% and 10.6%, grass carp skin gelatin is respectively containing 9.5% and 10.6% (Wang Weidong etc., the preparation of fishskin gelatin, characteristic and application, Food Science, 2009, 30(23): 484-488)], egg white, the clarification purification techniques of papain, but after removing haze active plant polyphenol, derive again the problem that removes again (the C.G.B Cole of remaining protein, the use of gelatin in wine fining, Proceeding of the SAAFost Technical Symposium, Beadle, Leigh P.Beer brewing system and method, US 5718161).
In aforementioned first field, at present the main Seveage method that adopts is the organic solvent sex change removal method of representative, proteinase hydrolization method, membrane separation process and macroporous absorbent resin adsorption method of separation deproteination matter (Lu Huiling etc., the progress that in plant polyose, albumen removes, research and development of natural products, 2008,20:185-189).Solvent denaturation take off albumen effect still can, but solvent consumption is large, separation difficulty, product loss and toxic solvent and corrosivity, and it is expensive, time-consuming, the feature of effort and danger be not suitable for production; Compared with taking off albumen with organic solvent sex change, proteinase hydrolization method is more promising, has economy, the advantage that fast, efficient, safe, product loss is little, but the comparatively strong caused scope of application of the selectivity in enzyme of mistake is limited; Membrane separation process effective area is large, filtering velocity fast, without phase-state change, the destruction of low-temperature operation to active ingredient is little and energy consumption is low, and can realize the separation of protein under protozoa system environment, also effectively can remove impurity by the long-pending product of efficient concentration richness.But produce just ground zero for Chinese medicine at present, need to improve and improve in equipment use efficiency and technology etc.; Macroporous resin adsorption protein isolate not only efficient, equipment is simple, easy to operate, be easy to automation, three expenses are conducive to environmental protection less, and yield is high, quality is good, leachate and ultimate constituent kind and relative amount completely the same, it is a kind of applicable large industrial method, but at present polymeric adsorbent (only having polarity and nonpolar two classes) of less types and adsorptive selectivity is poor, can not meet the needs to effective ingredients in plant separation well.
In aforementioned second field, in wine and fruit drink, the muddy main cause formed is the insoluble compound that haze active proteins and the effect of haze active plant polyphenol are formed, therefore usually need to remove haze active proteins, haze active plant polyphenol or remove the two (Kenneth A Leiper et al simultaneously, Optimising beer stabilisation by the sellective removal of tannoids and sensitive proteins, J of the institute of brewing, 2005:118-126).Industrial usual employing four kinds of methods remove haze active proteins: (1) silica-based adsorbent adsorbing and removing method; (2) PVPP-Si oxide mixed adsorbent removal method; (3) tannic acid deposition removal method and (4) papain hydrolysis removal method (Mustafa, R. et al, Beer stabilization thechnology-Clear a Mater of choice MBAA TQ, 2005,42(6): 332-338).First method adopts silica hydrosol, the dry colloidal sol of silica, imvites etc. are adsorbent, because its adsorptive selectivity difference causes also removing other active ingredients when removing haze active proteins (as local flavor protein, bubble and hold bubble ability protein and other active component) and cause product loss, also there is sedimentation slow, isolated by filtration difficulty and the problem (Georg that production efficiency is low and production cost is high, Luer et al Beer clarification aid based on silica xerogel with high filterability US 2010/0112132A1), second method adopts silica dry colloidal sol/PVPP mixed adsorbent (Polycar Plus 730), its adsorptive selectivity better and can remove haze active proteins and haze active plant polyphenol simultaneously, but still there is problem (the Chandra G et al of sedimentation and separation difficulty, Brewer ' Guardian sPVPP-the route to effective beer stabilization, May 2000:1-7, Mustafa R etal. Superior colloidal stabilization of beer by combined treatment with silica(xerogel) and PVPP, Polyclar plus 730, MBAA TQ, 2000,37(1): 113-118), the third method adds tannic acid in beer makes itself and haze active proteins form complex precipitate and remove, but deposit seed is tiny, consuming time and filtration is very difficult, excessive tannin remains in wine body and in turn introduces new haze active plant polyphenol, also harmful effect (Mustafa R et al A new direction in beer stabilization can be had to its color and luster, mouthfeel and fragrance, Inst Brew Africa Sect, Proc 7
thbrewing convention).4th kind of method adopts (fixing) papain or proline specific restriction endonuclease to make it lose haze active (Mustafa R et al haze active proteins degraded, Colloidal stabilization of beer, US 2003/0194477A1; Lopez; Michel, et al.Method for the prevention or reduction of haze in beverages, US 8119171), but can to the foaming of beer and hold bubble property have a negative impact.Carragheen and pectin deposition removal (Marangon M et al can be adopted for the haze active proteins in fruit juice, Protein removal fom Chardonnay juice by addition of carrageenan and pectin, Australian Journal of grape and wine research 2012,18:194-202), but also deposit the problem of the slow and isolated by filtration difficulty of sedimentation.
In aforementioned 3rd field, brewing industry extensively adopts the solution adding gelatin or fish glue (also Pro-rich and glutamic acid) by forming deposition removal haze active polyphenol at present, and make wine body become stable and color and luster is better, but the residue gelatin introduced in wine body and fish glue need to remove again, current employing tannic acid precipitation and silica-based adsorbent absorption remove gelatin again, have problems ditto described and add treatment process.
In sum, the technology focus removed of the protein in water-based fluid is just summed up in the point that improve the adsorptive selectivity of target protein, solve the aspects such as sedimentation separation difficulty and simplify processes technique.In recent years, basic research has disclosed the main adsorption mechanism such as Hydrogen Binding Adsorption, hydrophobic adsorbent and delocalizedπelectron absorption, and recognizes that the key obtaining sorbing material adsorptive selectivity is to guarantee the selectivity of its adsorption mechanism.With tannin be the plant polyphenol of representative can there is strong interaction with the haze active proteins of Pro-rich and glutamic acid and gelatin and there is compound, crosslinked formation is precipitated, its effect is fast and initial stage invertibity, be similar to antigen--the interactional selectivity of antibody and molecular recognition feature and hydrogen bond thereof and hydrophobic interaction essence also revealed, but when water-soluble tannin is directly used in the deposition removal of protein in water-based fluid, what inevitably there is compound sedimentation and separation difficulty and excessive tannin removes problem again.
Above-mentioned contradiction has just expedited the emergence of to be carried out insoluble or fixing (change) and changes process and make sorbing material by tannin, be used further to the technical scheme that protein selective in water-based fluid removes, fixing (change) technology of Here it is so-called tannin, (change) is fixed on insoluble carrier by tannin, both most of active group and the active sites of tannin had been retained, it is made still to have the very strong ability be combined with protein and metal ion, a series of properties that water-soluble tannin itself does not have can be obtained again, as mechanical performance and chemical stability etc.
United States Patent (USP) UP5912037 discloses a kind of technology at fixing (changes) tannin of silica xerogel particle in-situ epoxy activation, and gained contains tannin complexes can cut down the NTU turbidity that haze active proteins in beer, wine and fruit juice causes.European patent application EP0118990 then discloses a kind of means such as periodate oxidation and formaldehyde activation that adopt and tannin or polyphenol is fixed (change) in the technology of silica particles, can be used for cutting down white wine muddy.Above-mentioned technology achieves the insoluble of tannin, and what eliminate the impact on drinks local flavor, mouthfeel that directly uses tannic acid deposition removal haze active proteins to cause and excessive tannic acid removes operation again.But the particle characteristic of sorbing material makes it block filter and filtering velocity is improved very limited slowly, and a rear technology also needs preposition imvite pretreatment process just can reach good effect.
For adsorbent and the Problems existing in the application thereof of (change) tannin fixing on solid particle, another kind of tannin is fixed the form of (change) technological adjustment immobilization carrier and then is changed the application mode of fixing (change) tannin, Chinese patent CN1305559C discloses a kind of super big hole cellulose beads and fixes (change) tannin adsorbent and its preparation method and application, this technology uses wide material sources and skeleton has hydrophilic cellulose fixing (change) carrier as tannin, gained adsorbent can adopt packed column PROCESS FOR TREATMENT wine and reduce its EBC turbidity and EBC colourity, its turbidity and colourity cut down effect be better than the tannic acid precipitation method and can keep beer to greatest extent hold holding property of bubble and SASPL value, but Macroporous spherical cellulose manufacturing technique is numerous and diverse and the defect of cellulose its own mechanical intensity and resistance to acids and bases difference is also apparent.
Adopt above-mentioned tannin to fix sorbing material prepared by (change) change technology is except the protein removed for selective absorption in water-based fluid, also adsorbablely remove metal ion and organic pollution, thus there are the feature (Li Lu etc. of multiple adsorption function, the synthesis of new curing tannin resin and the Study on adsorption properties to Determination of Trace Palladium (II) thereof, Journal of Analytical Science, 2009,25(2): 193-196; Chen Jia letter etc., polyphenolic acid complex functionality macromolecular material is studied (I)-gallic acid and cellulosic lactate synthesis and product functional characteristic and is tested, chemistry of forest product and industry, and 2005,25(2): 6-10; Wang Yongmei etc., polyphenolic acid complex functionality macromolecular material research (II)-galloyl modified-cellulose synthesis and functional characteristic test thereof, chemistry of forest product and industry, 2005,27(2): 2-6; L.Liam; et al. Use of immobilized tann adsorbent for removal of Cr (VI) from water; Journal of radionalytical and chemistry, 1998,231 (1-2): 36-40; Zhong Cao Adsorption of Phenol on Bifunctional Resin and Granular Activated Carbon Preloaded by Tannic Acid, Advanced Materials Research, 2011,233-235:765-763).
Summary of the invention
Existing to protein adsorption in water-based fluid for overcoming, the deficiency of separation and removing sulfuldioxide, the invention provides a kind of preparation method of the sorbing material at nonwoven surface coupling tannin, the method with macromolecule nonwoven fabric for base material, carboxylic insatiable hunger is closed monomer-grafted to nonwoven surface by uv induction technology, recycling diamine and the condensation of carboxyl under catalyst action and introduce amido, then schiff bases reactive intermediates is translated into through aldehyde activation, utilize its coupling reaction in the solution that tannin coupling is fixed (change) in nonwoven surface, the sorbing material that the tannin removing non-coupling obtains nonwoven surface coupling tannin is cleaned finally by boiling water, and use it for the absorption of protein in water, be separated and remove.
Technical scheme of the present invention comprises the steps: the method in the Chinese patent (application number 201010559722.2) 1. applied for according to the present inventor, utilizes UV inductive technology at the carboxylic unsaturated monomer of nonwoven surface grafting to introduce carboxyl; 2. under catalyst action, be there is condensation reaction and introduce amido in gained nonwoven fabric graft product and diamine; 3. the amido introducing nonwoven fabric is converted into schiff bases reactive intermediates through aldehyde activation (mannich reaction); 4. utilize schiff bases reactive intermediates and tannin coupling reaction in the solution that tannin coupling is fixed (change) to nonwoven surface; 5. the tannin i.e. sorbing material of obtained described nonwoven surface coupling tannin of non-coupling is removed with boiling water cleaning; 6. gained sorbing material is dropped into containing in protein aqueous solution and model wine solution, under agitation adsorbing and removing protein.
According to technical scheme of the present invention, each step reaction principle involved in the present invention, for PP nonwoven fabric-acrylic acid (AA)-triethylene tetramine (TETA)-formaldehyde (HCHO) system, be expressed as follows (wherein PP-g-TETA-X is PP nonwoven fabric TETA schiff bases reactive intermediates):
The preparation method of the sorbing material at nonwoven surface coupling tannin provided by the invention, concrete operation step is as follows:
1) containing the glycerol polymerization of carboxyl unsaturated monomer in nonwoven surface
The method process nonwoven fabric of the Chinese invention patent (application number 201010559722.2) applied for according to the present inventor, prepare the grafting liquid of carboxylic unsaturated monomer and light/thermal initiator, and carry out nonwoven surface containing the UV induced graft polymerization of carboxyl unsaturated monomer and the purifying of graft product with 2-5 layer stack manner, then measure its carboxyl-content and water absorption rate by back titration method, and carry out FTIR, SEM and thermal analyses TG-DTG characterizes;
Nonwoven fabric used is synthesis or natural polymer nonwoven fabric, as polypropylene and PP nonwoven fabric, ethylene-propylene copolymer and EP nonwoven fabric, polyethylene and PE nonwoven fabric, polyester and PET or PBT nonwoven fabric, polyamide and PA nonwoven fabric, polyvinyl alcohol and PVA nonwoven fabric, polyimide nonwoven fabric, cellulosic nonwoven fabric or azelon nonwoven fabric.
Described carboxylic unsaturated monomer be in acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride one or more arbitrarily than mixture.
2) catalyzing and condensing of nonwoven fabric graft product and diamine
Nonwoven fabric graft product is put into by the solution of diamine, solvent and catalyst preparation or suspension, reflux condensation 2 ~ 8 hours at 100 ~ 160 DEG C, take out nonwoven fabric diamine amination crude product cyclic washing 3 times in distilled water, then absolute ethyl alcohol soxhlet type is used 2 ~ 24 hours, use distilled water quick wash subsequently 3 ~ 5 times, the nonwoven fabric diamine aminate of purifying is obtained again after 60 DEG C of dryings, measure its amine groups content, water absorption rate, and carry out FTIR, SEM and thermal analyses TG-DTG characterizes;
Wherein diamine is the polyethylene polyamine such as diethylenetriamine, triethylene tetramine; The mixture of one or more arbitrary proportions in the aliphatic diamines such as the aromatic diamines such as p-phenylenediamine (PPD), o-phenylenediamine, m-phenylene diamine (MPD) and ethylenediamine, butanediamine, hexamethylene diamine; The mol ratio of diamine and carboxyl is for being 5:1 ~ 30:1, preferably 10:1 ~ 20:1;
Described solvent is N, one or more arbitrarily than mixture in N-dimethylformamide (DMF), formamide, aromatic hydrocarbon, halogenated hydrocarbons, nonwoven fabric graft product quality (g) and solvent volume (mL) are than being 1:2 ~ 1:20, and preferably 1:4 ~ 15(adopts during liquid dihydric amine and also can not use solvent);
Described catalyst is the one in Lewis acid, Bronsted acid, heteropoly acid, and Lewis acid is AlCl
3.6H
2o or its analog, described catalyst amount is 1 ~ 10mol% of the total mole number of carboxyl, diamine, solvent and catalyst, preferably 2 ~ 5mol%;
Described setting-up point is 100 ~ 160 DEG C, preferably 120 ~ 140 DEG C, and condensation reaction time is 2 ~ 8 hours, preferably 3 ~ 5 hours, and described absolute ethyl alcohol extraction times is 2 ~ 24h, preferably 6 ~ 12 hours.
3) nonwoven fabric aminate is schiff bases reactive intermediates through aldehyde activating conversion and tannin coupling is fixed (change) on nonwoven fabric
The nonwoven fabric diamine aminate getting purifying to immerse in distilled water fully swelling 1 hour, then filter and after proceed to pH be 6.5 tanning solution in, slow dropping mass percentage concentration is the aldehydes activator solution of 25-80% and adds hot reflux 6 hours, product is soaked in boiling water and within 2 hours, washes away the tannin that (change) is fixed in non-coupling, the sorbing material of nonwoven surface coupling tannin is drying to obtain again, with its content of phenolic hydroxyl groups of Boehm titration measuring n in 60 DEG C
pand water absorption rate, and carry out FTIR, SEM and thermal analyses TG-DTG characterizes (mmol/g).
Wherein, tanning solution concentration is 5-50g/L, preferably 10-35g/L; Tanning solution volume (mL) and nonwoven fabric diamine aminate quality (g) are than being 5-50, preferably 10-30; Aldehydes activator solution volume (mL) and nonwoven fabric diamine aminate quality (g) are than being 2-20, preferably 5-15.
Described tanning solution distilled water prepare and use Bloomsbury smooth-to be adjusted to pH be 6.5 to Robison (B-R) cushioning liquid, described aldehydes activator is the mixture of one or more arbitrary proportions in formaldehyde, glutaraldehyde, oxazolidine or its polymerization or modified product, its concentration is determined according to its kind: the mass percentage concentration of formaldehyde is 37% usually, the mass percentage concentration of glutaraldehyde is the mass percentage concentration of 25% ， oxazolidine is 80%.
To gained nonwoven surface coupling tannin adsorptive material its content of phenolic hydroxyl groups of Boehm titration measuring n
pand water absorption rate, and carry out FTIR, SEM and thermal analyses TG-DTG characterizes (mmol/g).With batch determination of adsorption method sorbing material under magnetic agitation in water or the adsorbance Q of model wine Proteins In Aqueous Solutions (gelatin) and removal efficiency T, quantification of protein adopts the ninhydrin colour developing photometry after hydrolysis.
Principle of the present invention and concrete feature are: (1) utilizes modern industry to produce in a large number and the ripe macromolecule nonwoven fabric being applied to filter medium and earth working material is support material, give the speciality of sorbing material fiber-like adsorbent, thus overcome the tannin carrier macropore ball cellulose beads manufacture difficulty and the shortcoming of intensity and poor durability that prior art commonly uses, and obtain the flexibility advantage of high osmosis, high filtration stability, micron-sized strainability, the low filtered water stream pressure loss and end product application form; (2) utilize the carboxylic unsaturated monomer of uv induction technology grafting on nonwoven fabric and introduce carboxyl, and to be reacted by the catalyzing and condensing of itself and diamine and follow-up aldehyde activates the schiff bases reactive intermediates formed the coupling of tannin molecule is fixed (change) in nonwoven surface, be the selective absorption function that sorbing material gives to protein.Acrylic acid-grafted layer plays the wall effect between hydrophobic nonwoven fabric and adsorption activity tannin layer, its hydrophilic and water swellability makes coupling fix (change) tannin on it fully can enter protein solution, also to be conducive in water protein molecule to its surface diffusion into the surface, and then to be conducive to nonwoven surface coupling tannin catching and absorption protein in water.Tannin is the class plant polyphenol extracted from plant bark and fruit, and proline, glycine and glutamic acid units generation specificity polyphenol easily and in protein--protein hydrogen bonds, hydrophobic, the stacking cooperative interaction of π make protein optionally be adsorbed.The sterically hindered little Yi of glycine and tannin generation Hydrogenbond, proline makes protein molecule present variable and open space structure, can add the affinity of larger protein and tannin further, this principle has been succeeded application in traditional tannin tanning and beer clarification technique; (3) regulation and control of wall hydrophily and chemical micro-environment are realized by the adjustment of nonwoven fabric graft product carboxyl-content, degree of neutralization and amine groups content; (4) can be regulated and controled at the coupling effect of nonwoven surface and fixing content of phenolic hydroxyl groups tannin by the adjustment of each step reaction condition, and then regulate and control the hydrophily of sorbing material and the absorption property to protein thereof; (5) adsorption experiment selects the protein of this Pro-rich of gelatin and glutamic acid as model protein, can take into account the practicality of adsorbing and removing protein from water-based fluid in application background of the present invention; (6) the nonwoven surface coupling tannin adsorptive material adopting the present invention to prepare, the adsorption activity groups such as its rich surface phenolic hydroxy group, carboxyl and amido, also can be used for the adsorbing and removing that underwater gold belongs to the pollutant components such as ion, dyestuff and organic matter, also there is the ability that certain reduction plant base beverage forms inorganic salts muddiness and biological haze.
The advantage of the inventive method and described sorbing material is: (1) tannin coupled fixing (change) is in nonwoven surface, nonwoven fabric provides mechanical performance and large specific area, the tannin that coupling is fixed (change) then provides adsorption function, play the effect of composite adsorbing material performance complement, water-soluble, problem that tannin-protein complex sedimentation is slow and isolated by filtration is difficult that tannin self exists as adsorbent can be eliminated simultaneously, and continuous print packed column, bed absorption can be realized; (2) traditional microspheric or granular pattern coupling are fixed (change) tannin adsorptive material and change non-woven fabric type absorption filtering material into, can the multiple adsorption filtration application form such as supporting pillar, bed, plate, frame, felt, band, volume, cylinder; (3) sorbing material of the present invention also has certain adsorbing and removing ability to pollutant components such as the metal ion in water, dyestuff and organic matters; (4) raw material sources of sorbing material are wide, collapsible, cutting and easy to use, handling ease, combination property are excellent and applied widely, can be widely used in natural products deep processing, food, brewage, the absorption of light industry, chemical industry and protein in water-based fluid in the fields such as water treatment, be separated and remove; (5) this sorbing material hydrophily is better, and water absorption rate can more than 1000%; Its content of phenolic hydroxyl groups and water absorption rate are adjustable on a large scale, to protein, there is stronger adsorption capacity, when the concentration of gelatin in the aqueous solution or model wine is between 100-400mg/L, its equilibrium adsorption capacities, between 14.7-50.9mg/g, reaches adsorption equilibrium at 1 hours.
Accompanying drawing explanation
Fig. 1 is that the FTIR of PP nonwoven fabric and various material in the present invention composes schematic diagram, and in figure, 1 is PP nonwoven fabric; 2 is the acrylic acid-grafted product of PP nonwoven fabric; 3 is PP nonwoven fabric triethylene tetramine aminate; 4 is the sorbing material of PP nonwoven surface coupling tannin; 5 is the FTIR spectral line of tannin;
Fig. 2 is the SEM photo of PP nonwoven fabric in the present invention, left × 500 times, right 4000 times;
Fig. 3 is the SEM photo of the acrylic acid-grafted product of PP nonwoven fabric (embodiment 3) in the present invention, left × 500 times, right 4000 times;
Fig. 4 is the SEM photo of PP nonwoven fabric triethylene tetramine aminate (embodiment 3) in the present invention, left × 500 times, right 4000 times;
Fig. 5 is the SEM photo of the sorbing material (embodiment 5) of PP nonwoven surface coupling tannin in the present invention, left × 500 times, right 4000 times;
Fig. 6 is the SEM photo of (embodiment 7 adsorbs 120 points of kinds) after the sorbing material absorption gelatin of PP nonwoven surface coupling tannin in the present invention, left × 500 times, right 4000 times;
Fig. 7 is the thermal analyses TG/DTG spectrogram of each intermediate product in the present invention, and in figure, A is PP nonwoven fabric, and B is the acrylic acid-grafted product of PP nonwoven fabric (embodiment 3);
Fig. 8 is the thermal analyses TG/DTG spectrogram of each intermediate product in the present invention, and in figure, A is PP nonwoven fabric triethylene tetramine aminate (embodiment 3), and B is the sorbing material (embodiment 5) of PP nonwoven surface coupling tannin;
Fig. 9 is the thermal analyses TG/DTG spectrogram of each intermediate product in the present invention, and in figure, A is that PP nonwoven surface coupling tannin adsorptive material adsorbs gelatin (embodiment 7 adsorbs 120 points of kinds), B is tannin;
Figure 10 is the relation (embodiment 6) of sorbing material to the adsorbance Q of gelatin and removal efficiency T and gelatin solution pH value of PP nonwoven surface coupling tannin;
Figure 11 is the relation (embodiment 7) of sorbing material to the adsorbance Q of gelatin and removal efficiency T and adsorption time of PP nonwoven surface coupling tannin;
Figure 12 is the relation (embodiment 8) of sorbing material to the adsorbance Q of gelatin and removal efficiency T and gelatin solution concentration of PP nonwoven surface coupling tannin.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the invention will be further described, but content of the present invention is not limited to these embodiments.According to the embodiment of the present invention for enlightening; with reference to above-mentioned description; by those skilled in the art not departing from the technology of the present invention thought range; carry out some deductions, replacement and diversified change and amendment; all should be considered as belonging to protection scope of the present invention, the reagent that in embodiment, reagent is commercial reagent if no special instructions or prepares according to a conventional method.
embodiment 1:in the preparation method of the sorbing material of nonwoven surface coupling tannin, concrete operations are as follows:
(1) preparation of the acrylic acid-grafted product of PP nonwoven fabric
Carry out with reference to the method in Chinese patent application (application number 201010559722.2) " a kind of ion exchange nonwoven fabric with high carboxyl content and preparation method thereof ", concrete operations are as follows:
A, cut out round PP nonwoven fabric that a collection of diameter is 8cm (commercially available, specification: 10.5g/m
2, thickness 70.3 μm, water absorption rate is 36.1%), soak 12h in acetone, impurity such as removing surface and oil contaminant and auxiliary agent etc., drying for standby after taking out;
B, by acetone by 50%(percentage by volume) with distilled water be made into mixed solvent, adding acrylic acid, benzophenone and azodiisobutyronitrile, to be made into monomer solution for subsequent use, each component concentration is acrylic acid 50%(percentage by volume), benzophenone 25.0g/L and azodiisobutyronitrile 0.5g/L;
C, the PP nonwoven fabric of clean drying is placed in above-mentioned monomer solution soaks 1.5h, take out PP nonwoven fabric, be laid on glass surface ware so that 2-5 layer is stacking, with N logical after PE film (thickness is 23 μm) sealing
2after air-discharging, keep sealing state 500W uv light irradiation 1.5h (irradiation distance is 15cm); Then unpacking PE film, each layer nonwoven fabric is separated with distilled water immersion, put it in glass container, adding distil water boils 30 minutes, change and clean 24h under magnetic stirring after distilled water repeats to boil and thoroughly remove non-polymeric acrylic acid and homopolymers thereof, irradiation product, through 60 DEG C of dry constant weights, obtains the acrylic acid-grafted product of PP nonwoven fabric, measures its carboxyl-content by NaOH standard liquid back titration method.
Polypropylene (PP) nonwoven fabric that the present embodiment adopts, used is acrylic acid containing carboxyl unsaturated monomer, and the carboxyl-content Sg of the acrylic acid-grafted product of gained PP nonwoven fabric is 5.0mmol/g, and its water absorption rate is 759.9 %.
(2) preparation of PP nonwoven fabric triethylene tetramine aminate
Acrylic acid-grafted for PP nonwoven fabric product is put into by triethylene tetramine TETA and catalyst A lCl
3.6H
2condensation 6 hours at 100 DEG C in the solution of O preparation, by aminate distilled water cyclic washing 3 times after reaction terminates, with absolute ethyl alcohol soxhlet type 10 hours, use distilled water quick wash subsequently 5 times, the yellow PP nonwoven fabric triethylene tetramine aminate of purifying is obtained again, its amine groups content A in 60 DEG C of dryings
tETAfor 3.7mmol/g, water absorption rate 801.3 %;
Wherein the mol ratio of triethylene tetramine and carboxyl is the acrylic acid-grafted product quality (g) of 10:1, PP nonwoven fabric is 1:10, catalyst A lCl with triethylene tetramine volume (mL) ratio
3.6H
2the addition of O is the 1mol% of the total mole number of carboxyl, triethylene tetramine and catalyst;
(3) PP nonwoven fabric triethylene tetramine aminate is schiff bases reactive intermediates through aldehyde activating conversion and tannin coupling is fixed (change) on nonwoven fabric
PP nonwoven fabric triethylene tetramine aminate to be immersed in distilled water swelling 1 hour, proceed in the tannic acid solution (regulating pH to 6.5 with B-R cushioning liquid) that concentration is 35g/L after filtration, slow dropping mass concentration is 37% formalin, back flow reaction 6 hours, product soaks 2 hours in boiling water, and in being drying to obtain the sorbing material of the brownish red PP nonwoven surface coupling tannin of purifying in 60 DEG C, wherein tanning solution volume volume (mL) and PP nonwoven fabric triethylene tetramine aminate quality (g) are than being 10, formalin (mL) and PP nonwoven fabric triethylene tetramine aminate quality (g) are than being 5.
The sorbing material of gained PP nonwoven surface coupling tannin, its content of phenolic hydroxyl groups n
pfor 4.0mmol/g, water absorption rate is 967.0%.
(4) sorbing material of PP nonwoven surface coupling tannin is to the adsorption experiment of gelatin
1. to the absorption of gelatin in the aqueous solution
Get the sorbing material 0.1g of PP nonwoven surface coupling tannin for 25 mL 200 mg/L gelatin (food-grade Type Bs, isoelectric point 4.7-5.2) absorption of gelatin in the aqueous solution (pH is 6), adsorb 2 hours under 20 DEG C of magnetic agitation, filter out absorption raffinate after absorption, and add 20mL H wherein
2sO
4after at boiling water bath temperature, clear up 12 hours after, remain the concentration (with amino acid gauge) of gelatin with in ninhydrin colour developing spectrphotometric method for measuring absorption raffinate, the sorbing material recording coupling tannin is 23.5mg/g to the adsorbance Q of gelatin.
2. to the absorption of gelatin in model wine solution
The preparation of model wine solution: with 95% ethanol, pH be 6.2 distilled water and potassium hydrogen tartrate be mixed with model wine solution containing ethanol 12% (V/V) and potassium hydrogen tartrate 2g/L, its pH value is 3.7.
The sorbing material 0.1g getting PP nonwoven surface coupling tannin is in the model wine solution of 200 mg/L gelatin for 25 mL concentration, adsorbs 2 hours, filter out absorption raffinate, and add 20mL H wherein after absorption under 20 DEG C of magnetic agitation
2sO
4after at boiling water bath temperature, clear up 12 hours after, by the concentration (with amino acid gauge) remaining gelatin in ninhydrin colour developing spectrphotometric method for measuring absorption raffinate, the sorbing material recording coupling tannin is 14.7mg/g to the adsorbance Q of gelatin in model wine solution.
Change sorbing material into PP nonwoven fabric simultaneously, record it and only 4.2mg/g and 3.7mg/g is respectively to the adsorbance Q of the gelatin in the aqueous solution and model wine solution, show it to gelatin substantially without suction-operated.
embodiment 2:in the preparation method of the sorbing material of nonwoven surface coupling tannin, concrete operations are as follows:
(1) preparation of the acrylic acid-grafted product of PP nonwoven fabric
Carry out with reference to the method in Chinese patent application (application number 201010559722.2) " a kind of ion exchange nonwoven fabric with high carboxyl content and preparation method thereof ", concrete operations are with embodiment 1 step (1), the present embodiment adopts polypropylene (PP) nonwoven fabric, used is acrylic acid containing carboxyl unsaturated monomer, the carboxyl-content Sg of the acrylic acid-grafted product of gained PP nonwoven fabric is 6.1mmol/g, and its water absorption rate is 802.1 %.
(2) preparation of PP nonwoven fabric triethylene tetramine aminate
Acrylic acid-grafted for PP nonwoven fabric product is put into by triethylene tetramine TETA and catalyst A lCl
3.6H
2condensation 2 hours at 150 DEG C in the solution of O preparation, by aminate distilled water cyclic washing 3 times after reaction terminates, with absolute ethyl alcohol soxhlet type 6 hours, use distilled water quick wash subsequently 3 times, the yellow PP nonwoven fabric triethylene tetramine aminate of purifying is obtained again, its amine groups content A in 60 DEG C of dryings
tETAfor 4.2mmol/g, water absorption rate 846.4 %;
Wherein the mol ratio of triethylene tetramine and carboxyl is the acrylic acid-grafted product quality (g) of 15:1, PP nonwoven fabric is 1:13, catalyst A lCl with triethylene tetramine volume (mL) ratio
3.6H
2the addition of O is the 8mol% of the total mole number of carboxyl, triethylene tetramine and catalyst;
(3) PP nonwoven fabric triethylene tetramine aminate is schiff bases reactive intermediates through aldehyde activating conversion and tannin coupling is fixed (change) on nonwoven fabric
PP nonwoven fabric triethylene tetramine aminate to be immersed in distilled water swelling 1 hour, proceed in the tannic acid solution (regulating pH to 6.5 with B-R cushioning liquid) that concentration is 25g/L after filtration, slow dropping mass concentration is 37% formalin, back flow reaction 6 hours, product soaks 2 hours at product in boiling water, again in the sorbing material being drying to obtain the brownish red PP nonwoven surface coupling tannin of purifying in 60 DEG C, wherein tanning solution volume (mL) and PP nonwoven fabric triethylene tetramine aminate quality (g) are than being 20, formalin volume (mL) and PP nonwoven fabric triethylene tetramine aminate quality (g) are than being 7.
The sorbing material of gained PP nonwoven surface coupling tannin, its content of phenolic hydroxyl groups n
pfor 4.5mmol/g, water absorption rate is 1009.7%;
(4) sorbing material of PP nonwoven surface coupling tannin is to the adsorption experiment of gelatin
The adsorbance Q of sorbing material to gelatin middle in the aqueous solution and model wine solution recording PP nonwoven fabric coupling tannin by the method in embodiment 1 step (4) is respectively 25.5mg/g and 18.9mg/g.
Sorbing material is changed into the acrylic acid-grafted product of PP nonwoven fabric simultaneously, record it and only 7.3mg/g and 5.5mg/g is respectively to the adsorbance Q of the gelatin in the aqueous solution and model wine solution, show that it has certain adsorption capacity to gelatin, but far below the sorbing material of PP nonwoven fabric coupling tannin.
embodiment 3:in the preparation method of the sorbing material of nonwoven surface coupling tannin, concrete operations are as follows:
(1) preparation of the acrylic acid-grafted product of PP nonwoven fabric
Carry out with reference to the method in Chinese patent application (application number 201010559722.2) " a kind of ion exchange nonwoven fabric with high carboxyl content and preparation method thereof ", concrete operations are with embodiment 1 step (1), the present embodiment adopts polypropylene non-woven fabric, its FTIR spectral line is shown in spectral line 1 in Fig. 1, Fig. 2 is shown in by SEM photo, and thermal analyses TG-DTG curve is shown in Fig. 7 A; Used is acrylic acid containing carboxyl unsaturated monomer, the carboxyl-content Sg of the acrylic acid-grafted product of gained PP nonwoven fabric is 7.0mmol/g, its water absorption rate is 850.3 %, its FTIR spectrogram is shown in spectral line 2 in Fig. 1, characteristic absorption is coincide with literature value, Fig. 3 is shown in by its SEM photo, and its thermal analyses TG-DTG curve is shown in Fig. 7 B, and Thermal Decomposition Characteristics and literature value coincide;
(2) preparation of PP nonwoven fabric triethylene tetramine aminate
Acrylic acid-grafted for PP nonwoven fabric product is put into by triethylene tetramine TETA and catalyst A lCl
3.6H
2in the solution of O preparation, condensation 3 hours at 120 DEG C, after reaction terminates, aminate distilled water is washed 3 times, with absolute ethyl alcohol soxhlet type 8 hours, use distilled water quick wash subsequently 5 times, the yellow PP nonwoven fabric triethylene tetramine aminate of purifying is obtained again, its amine groups content A in 60 DEG C of dryings
tETAfor 5.1mmol/g, water absorption rate is 890.8%, and its FTIR spectral line is shown in that Fig. 4 is shown in by Fig. 1 spectral line 3, SEM photo, and its thermal analyses TG-DTG curve is shown in Fig. 8 A.
Wherein the mol ratio of triethylene tetramine and carboxyl is the acrylic acid-grafted product quality (g) of 20:1, PP nonwoven fabric is 1:15, catalyst A lCl with triethylene tetramine volume (mL) ratio
3.6H
2the addition of O is the 3.0mol% of the total mole number of carboxyl, triethylene tetramine and catalyst;
(3) PP nonwoven fabric triethylene tetramine aminate is schiff bases reactive intermediates through aldehyde activating conversion and tannin coupling is fixed (change) on nonwoven fabric
PP nonwoven fabric triethylene tetramine aminate is added q.s distilled water swelling 1 hour, proceed in the tannic acid solution (regulating pH to 6.5 with B-R cushioning liquid) that concentration is 15g/L after filtration, slow dropping mass concentration is 37% formalin, reflux 6 hours, product soaks 2 hours in boiling water, the sorbing material of the brownish red PP nonwoven surface coupling tannin of purifying is drying to obtain again in 60 DEG C, wherein tanning solution volume (mL) and PP nonwoven fabric triethylene tetramine aminate quality (g) are than being 30, formalin volume (mL) and PP nonwoven fabric triethylene tetramine aminate quality (g) are than being 10.
The sorbing material of gained PP nonwoven surface coupling tannin, its content of phenolic hydroxyl groups n
pfor 5.2mmol/g, water absorption rate is 1269.0%.
(4) sorbing material of PP nonwoven surface coupling tannin is to the adsorption experiment of gelatin
Record PP nonwoven fabric coupling tannin adsorptive material by the method in embodiment 1 step (4) and 33.2mg/g and 24.9mg/g is respectively to the gelatin adsorbance Q in the aqueous solution and model wine solution.
Sorbing material is changed into the acrylic acid-grafted product of PP nonwoven fabric simultaneously, record it and only 8.6mg/g and 6.5mg/g is respectively to the adsorbance Q of the gelatin in the aqueous solution and model wine solution, show that it has certain adsorption capacity to gelatin, but far below PP nonwoven fabric coupling tannin adsorptive material.
embodiment 4:repeat embodiment 3, just change the concentration of tanning solution in step (3) into 35g/L, the sorbing material of gained PP nonwoven surface coupling tannin, its content of phenolic hydroxyl groups n
pfor 6.6mmol/g, water absorption rate is 1395.3.7%, records it and is respectively 50.9mg and 43.4mg/g to gelatin adsorbance Q in the aqueous solution and model wine solution.
embodiment 5:repeat embodiment 3, just by formalin volume (mL) in step (3) with PP nonwoven fabric triethylene tetramine aminate quality (g) than being adjusted to 15, the sorbing material of gained PP nonwoven surface coupling tannin, its content of phenolic hydroxyl groups n
pfor 5.9mmol/g, water absorption rate is 1344.4%, and its FTIR spectral line is shown in that Fig. 5 is shown in by Fig. 1 spectral line 4, SEM photo, and thermal analyses TG-DTG curve is shown in Fig. 8 B, records it and is respectively 46.9mg/g and 37.4mg/g to the adsorbance Q of gelatin in the aqueous solution and model wine solution.
embodiment 6:method is with embodiment 5, just by the pH value of aqueous gelatin solution in step (4) furnishing 5 respectively, 6,7 and 8, record it and 42.0,46.9,35.9 and 33.3mg/g are respectively to the adsorbance Q of gelatin in the aqueous solution, the relation of Q and T and aqueous gelatin solution pH value is shown in Figure 10, and when result display aqueous gelatin solution pH value is between 5-6, Q and T is comparatively large, maximumly can reach 46.9mg/g and 93.8% (when pH is 6) respectively.
embodiment 7:method is with embodiment 5, just adsorption time in step (4) is set as 5,10,20,30,60 and 120 minutes respectively, record it and 29.8,31.8,36.7,46.6,45.5 and 46.7mg/g are respectively to the adsorbance Q of gelatin in the aqueous solution, the relation of Q and T and adsorption time is shown in Figure 11, result display reaches adsorption equilibrium substantially to 1 hours that is adsorbed on of gelatin, adsorb 120 points of kinds and after drying process, Fig. 6 is shown in by its SEM photo, thermal analyses TG-DTG curve is shown in Fig. 9 A.
embodiment 8:method is with embodiment 1, just gelatin solution concentration in step (4) is set as 50,100,200,300 and 400mg/L respectively, record it and 10.7,23.0,33.4,47.2 and 48.7mg/g are respectively to the adsorbance Q of gelatin in the aqueous solution, the relation of Q and T and gelatin solution concentration is shown in Figure 12, when result display aqueous gelatin solution concentration increases, its Q increases, but T reduces to some extent.
embodiment 9:in the preparation method of the sorbing material of nonwoven surface coupling tannin, concrete operations are as follows:
(1) preparation of ethylene-propylene copolymer nonwoven fabric methacrylic acid graft product
With reference to Chinese patent application (application number 201010559722.2) " a kind of ion exchange nonwoven fabric with high carboxyl content and preparation thereof
Method " in method carry out, concrete operations with embodiment 1 step (1), the present embodiment adopt ethylene-propylene copolymer nonwoven fabric (commercially available, specification: 12.5g/m
2, thickness 74.5 μm, water absorption rate is 50.1%), be methacrylic acid containing carboxyl unsaturated monomer, the carboxyl-content Sg of the acrylic acid-grafted product of gained EP nonwoven fabric is 5.1mmol/g, and its water absorption rate is 797.1%;
(2) preparation of ethylene-propylene copolymer nonwoven fabric p-phenylenediamine (PPD) aminate
EP nonwoven fabric methacrylic acid graft product is put into by p-phenylenediamine (PPD), DMF DMF and catalyst A lCl
3.6H
2in the solution of O or suspension, condensation 5 hours at 140 DEG C, by EP nonwoven fabric p-phenylenediamine (PPD) amination crude product cyclic washing 3 times in distilled water after reaction terminates, then absolute ethyl alcohol soxhlet type is used 12 hours, use distilled water quick wash subsequently 4 times, the darkviolet EP nonwoven fabric p-phenylenediamine (PPD) aminate of purifying is obtained again, its amine groups content A after 60 DEG C of dryings
pPDfor 3.8mmol/g, water absorption rate is 1381.4%;
Wherein the mol ratio of p-phenylenediamine (PPD) and carboxyl is 10:1, EP nonwoven fabric methacrylic acid graft product quality (g) and N, N-dimethylformamide DMF volume (mL) is than being 1:4, the addition of catalyst is the 5mol% of the total mole number of carboxyl, p-phenylenediamine (PPD), DMF and catalyst;
(3) EP nonwoven fabric p-phenylenediamine (PPD) aminate is schiff bases reactive intermediates through aldehyde activating conversion and tannin coupling is fixed (change) on nonwoven fabric
EP nonwoven fabric p-phenylenediamine (PPD) product to be immersed in distilled water swelling 1 hour, proceed in the tannic acid solution (regulating pH to 6.5 with B-R cushioning liquid) that concentration is 25g/L after filtration, slow dropping mass concentration is 37% formalin, reflux 6 hours, product soaks 2 hours in boiling water, the sorbing material of mauve EP nonwoven surface coupling tannin is drying to obtain again in 60 DEG C, wherein tanning solution volume (mL) and EP nonwoven fabric p-phenylenediamine (PPD) aminate quality (g) are than being 25, formalin volume (mL) and EP nonwoven fabric p-phenylenediamine (PPD) aminate quality (g) are than being 12.
The sorbing material of gained EP nonwoven surface coupling tannin, its content of phenolic hydroxyl groups n
pfor 5.7mmol/g, water absorption rate is 1197.3%.
(4) sorbing material of EP nonwoven surface coupling tannin is to the adsorption experiment of gelatin
Method, with embodiment 1, records gelatin adsorbance Q in its aqueous solution and model wine solution and is respectively 29.5mg/g and 21.7mg/g.
embodiment 10:repeat embodiment 3, be just the II Xing oxazolidine solution that 37% formalin changes 80% into by mass concentration, and Kong oxazolidine liquor capacity (mL) and PP nonwoven fabric triethylene tetramine aminate quality (g) are than being 5, the sorbing material of gained PP nonwoven surface coupling tannin, its content of phenolic hydroxyl groups n
pfor 5.4mmol/g, water absorption rate is 1015.8%.It is respectively 35.7mg/g and 27.1mg/g to the adsorbance Q of gelatin in the aqueous solution and model wine solution.
embodiment 11:repeat embodiment 3, be just the glutaraldehyde solution that 37% formalin changes 25% into by mass concentration, and control glutaraldehyde solution volume (mL) and PP nonwoven fabric triethylene tetramine aminate quality (g) than being 10, the sorbing material of gained PP nonwoven surface coupling tannin, its content of phenolic hydroxyl groups n
pfor 5.5mmol/g, water absorption rate is 989.7%.It is respectively 39.1mg/g and 30.2mg/g to the absorption Q of gelatin in the aqueous solution and model wine solution.
embodiment 12:repeat embodiment 9, be just that 37% formalin changes the II Xing oxazolidine solution of 80% and the glutaraldehyde solution of 25% respectively into by mass concentration, and Kong oxazolidine liquor capacity (mL) and EP nonwoven fabric p-phenylenediamine (PPD) aminate quality (g) are than being 5, glutaraldehyde solution volume (mL) and EP nonwoven fabric p-phenylenediamine (PPD) aminate quality (g) are than being 10, the sorbing material of gained PP nonwoven surface coupling tannin, its content of phenolic hydroxyl groups n
pbe respectively 5.8mmol/g and 6.0mmol/g, water absorption rate is respectively 998.1% and 956.3%.Record it and 38.4mg/g (29.7mg/g) and 41.2mg/g (33.5mg/g) is respectively to the adsorbance Q of gelatin in the aqueous solution (model wine solution).
Above-described embodiment result shows: nonwoven fabric introduces carboxyl after the grafting of uv induction carboxyl unsaturated monomer, and carboxyl is a kind of anionic hydrophilic radical, has very strong water absorbing capacity.After the grafting of carboxyl unsaturated monomer, nonwoven fabric water absorption rate rises to 850.3% (embodiment 3 acrylic acid-grafted product) from 38.1%.The carboxyl introduced obtains aminate with triethylene tetramine condensation again, condensation reaction only consumes part carboxyl and introduces another kind of hydrophilic radical amido again, the triethylene tetramine aminate water absorption rate formed is 890.8%, and this two-step reaction makes nonwoven surface change from hydrophobic surface to hydrophilic surface.After further coupling tannin, amido is consumed and defines comparatively fine and close tannin cover layer due to tannin coupling reaction, and the content of phenolic hydroxyl groups n that (change) tannin is introduced is fixed in its water absorption rate and coupling
prelevant etc. factor, absorbing water rate usually can more than 1000% (embodiment 3 is 1269.0%), and therefore the present invention can obtain n
pthe sorbing material adjustable on a large scale with hydrophily.
As shown in Figure 1, the sorbing material (spectral line 4) of PP nonwoven fabric (spectral line 1), the acrylic acid-grafted product of embodiment 1 PP used nonwoven fabric (spectral line 2), PP nonwoven fabric triethylene tetramine aminate (spectral line 3), PP nonwoven surface coupling tannin and the FTIR spectral line of tannin (spectral line 5) are carried out superposition contrast.Can find spectral line 2 to have occurred carboxyl-OH stretching vibration peak and C=O stretching vibration peak, illustrate that acrylic acid is successfully grafted to PP nonwoven surface.Occur in spectral line 3 belonging to triethylene tetramine aminate N-H, the acid amides C=O stretching vibration infrared absorption peak formed after C-N stretching vibration and the condensation of amine carboxylic, all illustrated that triethylene tetramine take part in aminating reaction really.Spectral line 4 is FTIR spectral lines of fixing (change) tannin adsorptive material, all occurs each characteristic IR absorbance peaks corresponding with tannin FTIR spectral line, illustrates that the certain coupling of tannin molecule fixes (change) in PP nonwoven surface.
Fig. 2 is the SEM photo of PP nonwoven fabric, its any surface finish and uniform color, fibre diameter about 27.4 μm.Acrylic acid-grafted rear fiber becomes coarse, and diameter is slightly increased to 32.7 μm (Fig. 3).Fig. 4 is the SEM photo of triethylene tetramine aminate, and after aminating reaction, the package action of triethylene tetramine makes PP fiber surface occur equally distributed projection, and surface roughness declines to some extent, and fibre diameter is increased to 39.7 μm.Then there is obvious fold (Fig. 5) in the PP fiber surface of coupling is fixed (change) tannin.The fiber morphology reacting PP nonwoven fabric accordingly to each step also there occurs corresponding change, and this also shows the successful realization of each step reaction in the sorbing material preparation of PP nonwoven surface coupling tannin.
Fig. 7-9 is thermal analyses TG/DTG curves of PP nonwoven surface coupling tannin adsorptive material and raw materials and each intermediate product, along reaction sequence prepared by the even tannin adsorptive material of aforementioned PP nonwoven surface diazonium, its TG/DTG curve respectively walking the acrylic acid-grafted product of product P P nonwoven fabric-PP nonwoven fabric-PP nonwoven fabric triethylene tetramine aminate-PP nonwoven surface coupling tannin adsorptive material all there occurs corresponding change, the thermal decomposition peak of the acrylic acid-grafted product of PP nonwoven fabric has been there is in Fig. 7 B, the thermal decomposition peak of nonwoven fabric triethylene tetramine aminate and carboxyl condensation product has been there is in Fig. 8 A, the thermal decomposition peak relevant to tannin has been there is in Fig. 8 B, the DTG curve that particularly (change) tannin adsorptive material is fixed in coupling only shows decomposition temperature at the beginning of and the close pyrolysis peak of tannin, illustrate that the thermal decomposition of coupling tannin adsorptive material is the result that the fuel factor of fixing (change) tannin molecule by PP nonwoven fabric and coupling superposes.TG/DTG analyzes institute and obtains the successful realization that the above results proves that in the sorbing material preparation of PP nonwoven surface coupling tannin, each step is reacted again.
After coupling tannin adsorptive material absorption gelatin, there is belonging to respectively N-H in gelatin amide I at its FTIR spectral line and stretched or O-H stretching vibration peak, acid amides
,-CH
2-or CH
3-flexural vibrations peak, and belong to the CH of proline
2rocking vibration, acid amides
in C-N-C stretching vibration or C-O stretching vibration peak, these results all illustrate that fixing (change) tannin creates absorption to the gelatin molecule in the aqueous solution.Secondly, in SEM photo (Fig. 6) after coupling tannin adsorptive material absorption gelatin, occur that sheet connects at PP non-woven fabrics fiber weld, and define the different different wart like structure of obvious tannin wrappage before absorption at fiber surface, these irregular projections are distributed in PP fiber peripheral, and fibre diameter slightly increases than before absorption.Besides, thermal analyses TG/DTG curve after the sorbing material absorption gelatin of the PP nonwoven surface coupling tannin shown in Fig. 9 A is compared with the curve (Fig. 8 B) before absorption, although thermal decomposition peak does not have too large change, but each Thermal Decomposition Characteristics peak temperature is all significantly increased, the T of coupling is fixed (change) tannin
10, T
30, T
50389.3,458.4 and 481.4 DEG C are risen to respectively from 300.4,437.5 and 474.8 DEG C, can think that the rear sample heat endurance of absorption increases, the heat endurance of this and gelatin matches higher than the rule of tannin, and the absorption of tannin to gelatin molecule realizes also can to illustrate that coupling is fixed (change) thus.The above results all confirms that PP nonwoven surface coupling tannin adsorptive material creates strong suction-operated to the gelatin in the aqueous solution.
The mode of action that coupling is fixed (change) between tannin to protein (gelatin) molecule is similar with the interaction mechanism of protein (gelatin) molecule to free tannin, is also collaborative by hydrogen bond, hydrophobic effect, hydrophobic-hydrogen bond and absorption to protein (gelatin) molecule is reached in the stacking effect of π.Coupled fixing (changes) to drive by " hydrophobic effect " in tannin of PP nonwoven surface and is bound by the protein that can move freely in solution (gelatin) molecular beam, and adsorbs by " gloves-hand " model realization of combining closely.
Model protein gelatin for adsorbing in the present invention is Type B gelatin, its isoelectric point between 4.7-5.2, when its pH value of water solution is lower, the positive charge-NH on its molecule
3 +concentration is comparatively large, is conducive to fixing (change) tannin with coupling and interacts, this just gained sorbing material of the present invention be reason (Figure 10) larger to gelatin adsorbance in the aqueous gelatin solution of 5-6 at pH.
Tannin is a kind of water-soluble plant polyphenol, coupling is fixed (change) afterwards its its molecular motion ability usually can be subject to certain constraint.But tannin coupled fixing (change) is on the acrylic acid-grafted layer and triethylene tetramine amination layer of the imbibition of hydrophily strong also energy in the present invention, coupling is fixed (change), and tannin layer still has stronger water absorption and swelling, fully can stretch and reduce sterically hindered, the contact surface area that increases protein (gelatin) in itself and water that contact with protein in water (gelatin), and under superficial layer can be played to a certain extent tannin molecule to the suction-operated of protein (gelatin).PP nonwoven fabric is through each step chemical reaction and fix (change) the coupling of tannin, its surface changes from from hydrophobicity to hydrophilic surface, be conducive to the diffusion of protein in water (gelatin) molecule to its surface, be conducive to the coupling of PP nonwoven surface and fix (change) tannin catching and absorption protein (gelatin) molecule, make this material can reach adsorption equilibrium (Figure 11) fast to the absorption of gelatin.
In the aqueous solution, the concentration of model protein (gelatin) directly has an impact (Figure 11) to the adsorptivity of the peaceful sorbing material of PP nonwoven surface coupling receipts or other documents in duplicate, along with the increase of gelatin concentration, sorbing material increases to some extent the adsorbance Q of gelatin but T then decreases.When gelatin solution concentration is increased to 400mg/L from 50mg/L, its Q is increased to 48.0% from 10.7%, but T is reduced to 48.0%(Figure 12 from 85.5%).
Claims (8)
1. the preparation method at the sorbing material of nonwoven surface coupling tannin, it is characterized in that: with macromolecule nonwoven fabric for carrier, by uv induction technology, carboxylic unsaturated monomer is grafted to nonwoven surface, recycling diamine and the condensation reaction of carboxyl under catalyst action and introduce amido, then aldehyde activation method is utilized to be translated into schiff bases reactive intermediates, utilize its coupling reaction in the solution that tannin coupling is fixed to nonwoven surface, namely the tannin removing non-coupling finally by boiling water cleaning obtains the sorbing material at nonwoven surface coupling tannin,
The concrete operations of said method are as follows:
(1) containing the glycerol polymerization of carboxyl unsaturated monomer in nonwoven surface
Utilize the carboxylic unsaturated monomer of uv induction technology grafting on nonwoven fabric to introduce carboxyl, the purified rear back titration method of graft product measures its carboxyl-content and water absorption rate, and carries out FTIR, SEM and thermal analyses TG-DTG characterizes;
(2) catalyzing and condensing of nonwoven fabric graft product and diamine
Nonwoven fabric graft product is put into by diamine, in the solution of solvent and catalyst preparation or suspension, reflux condensation 2 ~ 8 hours at 100 ~ 160 DEG C, take out nonwoven fabric diamine amination crude product cyclic washing 3 times in distilled water, then absolute ethyl alcohol soxhlet type is used 2 ~ 24 hours, use distilled water quick wash subsequently 3 ~ 5 times, the nonwoven fabric diamine aminate of purifying is obtained again after 60 DEG C of dryings, measure its amine groups content and water absorption rate, and carry out FTIR, SEM and thermal analyses TG-DTG characterizes, wherein the mol ratio of diamine and carboxyl is 5:1 ~ 30:1, nonwoven fabric graft product quality and solvent volume are than being 1:2 ~ 1:20, the addition of catalyst is carboxyl, diamine, 1 ~ 10% of the total mole number of solvent and catalyst,
(3) nonwoven fabric diamine aminate is schiff bases reactive intermediates through aldehyde activating conversion and tannin coupling is fixed (change) on nonwoven fabric
The nonwoven fabric diamine aminate getting purifying to immerse in distilled water fully swelling 1 hour, then filter and proceed to that pH is 6.5, concentration is in the tanning solution of 5-50g/L, slow dropping mass percentage concentration is the aldehydes activator solution of 25-80% and adds hot reflux 6 hours, product is soaked in boiling water and within 2 hours, washes away the tannin that (change) is fixed in non-coupling, the sorbing material of nonwoven surface coupling tannin is drying to obtain again, with its content of phenolic hydroxyl groups of Boehm titration measuring n in 60 DEG C
pand water absorption rate, and carry out FTIR, SEM and thermal analyses TG-DTG characterizes (mmol/g);
Wherein, tanning solution volume and nonwoven fabric diamine aminate mass ratio are 5-50, and aldehydes activator solution volume and nonwoven fabric diamine aminate mass ratio are 2-20;
Described tanning solution distilled water prepare and use Bloomsbury smooth-to be adjusted to pH be 6.5 to Robison (B-R) cushioning liquid, described aldehydes activator is the mixture of one or more arbitrary proportions in formaldehyde, glutaraldehyde, oxazolidine and their polymerization or modified product.
2., according to claim 1 in the preparation method of the sorbing material of nonwoven surface coupling tannin, it is characterized in that nonwoven fabric is the one in polypropylene non-woven fabric, ethylene-propylene copolymer nonwoven fabric, polyethylene nonwoven, polyester non-woven fabric, polyamide nonwoven fabric, polyvinyl alcohol nonwoven fabric, polyimide nonwoven fabric, cellulosic nonwoven fabric, azelon nonwoven fabric.
3. according to claim 1 in the preparation method of the sorbing material of nonwoven surface coupling tannin, it is characterized in that: carboxylic unsaturated monomer is the mixture of one or more in acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride.
4., according to claim 2 in the preparation method of the sorbing material of nonwoven surface coupling tannin, it is characterized in that described diamine is the mixture of one or more in p-phenylenediamine (PPD), o-phenylenediamine, m-phenylene diamine (MPD), ethylenediamine, butanediamine, hexamethylene diamine.
5., according to claim 2 in the preparation method of the sorbing material of nonwoven surface coupling tannin, it is characterized in that catalyst is the one in Lewis acid, Bronsted acid, heteropoly acid.
6. according to claim 2 in the preparation method of the sorbing material of nonwoven surface coupling tannin, it is characterized in that: solvent is N, the mixture of one or more in N-dimethylformamide, formamide, aromatic hydrocarbon, halogenated hydrocarbons, adopts during liquid dihydric amine and also can not use solvent.
7. according to claim 2 in the preparation method of the sorbing material of nonwoven surface coupling tannin, it is characterized in that: aldehyde activator is formaldehyde, glutaraldehyde, oxazolidine or its polymerization or the mixture of one or more of modified product.
8. the sorbing material of the nonwoven surface coupling tannin obtained in the preparation method of the sorbing material of the sorbing material of nonwoven surface coupling tannin described in claim 1.
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| CN108752577B (en) * | 2018-06-25 | 2020-07-28 | 烟台大学 | Auxiliary agent for inhibiting tannin diffusion in wood and use method thereof |
| CN108745320B (en) * | 2018-06-28 | 2021-03-09 | 西南科技大学 | Preparation method of nano gelatin/polymer composite fiber tape based on uranium extraction from seawater |
| CN116328719A (en) * | 2021-12-22 | 2023-06-27 | 湖南中烟工业有限责任公司 | Phenolic hydroxyl modified activated carbon and preparation method and application thereof |
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| US4090919A (en) * | 1976-01-29 | 1978-05-23 | Tanabe Seiyaku Co., Ltd. | Water-insoluble tannin preparation for immobilization of proteins |
| CN1410157A (en) * | 2002-11-27 | 2003-04-16 | 四川大学 | Collagen fiber solidified tannin adsorptive material and its preparation method and its adsorption and separation of metallic ion |
| CN1644145A (en) * | 2005-01-14 | 2005-07-27 | 张小强 | Wet nonwoven towel containing tannic acid |
| CN1657157A (en) * | 2004-12-08 | 2005-08-24 | 华东理工大学 | Super large pore ball shaped cellulose fixed tannin adsorbent and its preparation method and application |
| CN102102295A (en) * | 2010-11-26 | 2011-06-22 | 昆明理工大学 | Ion exchange nonwoven fabric with high carboxyl content and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4090919A (en) * | 1976-01-29 | 1978-05-23 | Tanabe Seiyaku Co., Ltd. | Water-insoluble tannin preparation for immobilization of proteins |
| CN1410157A (en) * | 2002-11-27 | 2003-04-16 | 四川大学 | Collagen fiber solidified tannin adsorptive material and its preparation method and its adsorption and separation of metallic ion |
| CN1657157A (en) * | 2004-12-08 | 2005-08-24 | 华东理工大学 | Super large pore ball shaped cellulose fixed tannin adsorbent and its preparation method and application |
| CN1644145A (en) * | 2005-01-14 | 2005-07-27 | 张小强 | Wet nonwoven towel containing tannic acid |
| CN102102295A (en) * | 2010-11-26 | 2011-06-22 | 昆明理工大学 | Ion exchange nonwoven fabric with high carboxyl content and preparation method thereof |
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